# US 2014/0155566 A1 · Compounds containing alkyl-cyano-borate or alkyl-cyano-fluoroborate anions

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- Number: US 2014/0155566 A1
- Document ID: US20140155566A1
- Status: Published application
- Kind: A1
- Application number: 14/131,990
- Filed: 2012-07-06
- Published: 2014-06-05
- Earliest claimed: 2011-07-15
- Assignees: Merck Patent GmbH
- Inventors: Nikolai (Mykola) Ignatyen; Michael Schulte; Kentaro Kawata; Tomohisa Goto; Jan Sprenger; Maik Finze; Walter Frank
- Web page: https://patentgrep.com/patent/US20140155566A1

## CPC

- H01G 9/2013: {the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide}
- C07F 5/02: Boron compounds
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0568: characterised by the solutes
- H01M 14/005: {Photoelectrochemical storage cells (light sensitive devices H01G9/20, semiconductors sensitive to light H10F)}
- Y02E 10/542: Dye sensitized solar cells
- Y02E 60/10: Energy storage using batteries
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The invention relates to new compounds containing alkyl/alkenyl-cyano-borate or alkyl/alkenyl-cyano-fluoroborate anions, their preparation and their use, in particular as part of electrolyte formulations for electrochemical or optoelectronic devices.

## Claims

### Claim 1

Compounds of formula I
[Kt]z+z[(R1)4−x−y−vB(CN)x(NC)yFv]− I
in which
R1 each independently denotes
a straight-chain or branched alkyl group having 1 to 20 C atoms, which optionally may contain at least one Cl, Br or I atom, at least one CN group and/or one or more oxygen or sulphur atoms,
a straight-chain or branched alkenyl group having 2 to 20 C atoms having one or more double bonds, which optionally may contain at least one Cl, Br or I atom and/or one or more oxygen or sulphur atoms,
a straight-chain or branched alkinyl group having 1 to 20 C atoms having one or more triple bonds, which optionally may contain at least one Cl, Br or I atom and/or one or more oxygen or sulphur atoms and optionally may have a double bond,
or unsubstituted phenyl,
z is 1, 2, 3 or 4, x is 1, 2 or 3, y is 0, 1 or 2, v is 0, 1 or 2 and the sum of x+y+v is 2 or 3 and
in which Ktz+ denotes
an inorganic cation selected from the group of NO+, H+, Li+, Na+, K+, Rb+, Cs+, or Mg2+, Cu+, Cu2+, Zn2+, Ag+, Ca2+, Y+3, Yb+3, La+3, Sc+3, Ce+3, Nd+3, Tb+3, Sm+3 or complex (ligands containing) metal cations which include rare-earths, transitions or noble metals like rhodium, ruthenium, iridium, palladium, platinum, osmium, cobalt, nickel, iron, chromium, molybdenum, tungsten, vanadium, titanium, zirconium, hafnium, thorium, uranium, gold,
or an organic cation selected from the group of
a tritylium cation, in which the phenyl groups may be substituted by straight-chain or branched alkyl groups having 1 to 20 C atoms, straight-chain or branched alkenyl having 2 to 20 C atoms and one or more double bonds or straight-chain or branched alkynyl having 2 to 20 C atoms and one or more triple bonds,
an oxonium cation of formula (1) or a sulfonium cation of formula (2))
[(Ro)3O]+ (1))
[(Ro)3S]+ (2),
where Ro each independently of one another denotes a straight-chain or branched alkyl group having 1-8 C atoms, non-substituted phenyl or phenyl which is substituted by R1*, OR′, N(R′)2, CN or halogen and in case of sulfonium cations of formula (2) additionally denotes each independently (R′″)2N and R′ is independently of each other H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl, R1* is independently of each other non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and R′″ is independently of each other straight-chain or branched C1 to C6 alkyl;
an ammonium cation, which conforms to the formula (3)
[NR4]+ (3),
where
R in each case, independently of one another, denotes
H, OR′, N(R′)2, with the proviso that a maximum of one R in formula (3) is OR′ or N(R′)2,
straight-chain or branched alkyl having 1-20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, where one or two R may be fully substituted by halogens, in particular —F and/or —Cl, and one or more of the substituents R may be partially substituted by halogens, in particular —F and/or —Cl, and/or by —OH, —OR′, —CN, —N(R′)2, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′)2, —SO2N(R′)2, —C(O)X, —SO2OH, —SO2X, —NO2, —SR′, —S(O)R′, —SO2R′ and where one or two non-adjacent carbon atoms in R which are not in the α-position may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —SO2O—, —C(O)—, —C(O)O—, —N+(R′)2—, —P(O)R′O—, —C(O)NR′—, —SO2NR′—, —OP(O)R′O—, —P(O)(N(R′)2)NR′—, —P(R′)2═N— or —P(O)R′— where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and X each independently is halogen;
a phosphonium cation, which conforms to the formula (4)
[P(R2)4]+ (4),
where
R2 in each case, independently of one another, denotes
H, OR′ or N(R′)2,
straight-chain or branched alkyl having 1-20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms,
where one or two R2 may be fully substituted by halogens, in particular —F and/or —Cl, and one or more of the substituents R2 may be partially substituted by halogens, in particular —F and/or —Cl, and/or by —OH, —OR′, —CN, —N(R′)2, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′)2, —SO2N(R′)2, —C(O)X, —SO2OH, —SO2X, —NO2, —SR′, —S(O)R′, —SO2R′ and where one or two non-adjacent carbon atoms in R2 which are not in the α-position may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —SO2O—, —C(O)—, —C(O)O—, —N+(R′)2—, —P(O)R′O—, —C(O)NR′—, —SO2NR′—, —OP(O)R′O—, —P(O)(N(R′)2)NR′—, —P(R′)2═N— or —P(O)R′— where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and X each independently is halogen;
a uronium cation, which conforms to the formula (5)
[C(NR3R4)(OR5)(NR6R7)]+ (5),
where
R3 to R7 each, independently of one another, denote
H, where H is excluded for R5,
straight-chain or branched alkyl having 1 to 20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, where one or two of the substituents R3 to R7 may be fully substituted by halogens, in particular —F and/or —Cl, and one or more of the substituents R3 to R7 may be partially substituted by halogens, in particular —F and/or —Cl, and/or by —OH, —OR′, —N(R′)2, —CN, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′)2, —SO2N(R′)2, —C(O)X, —SO2OH, —SO2X, —SR′, —S(O)R′, —SO2R′, —NO2 and where one or two non-adjacent carbon atoms in R3 to R7 which are not in the α-position may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —SO2O—, —C(O)—, —C(O)O—, —N+(R′)2—, —P(O)R′O—, —C(O)NR′—, —SO2NR′—, —OP(O)R′O—, —P(O)(N(R′)2)NR′—, —P(R′)2═N— or —P(O)R′— where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and X each independently is halogen;
a thiouronium cation, which conforms to the formula (6)
[C(NR3R4)(SR5)(NR6R7)]+ (6),
where
R3 to R7 each, independently of one another, denote
H, where H is excluded for R5,
straight-chain or branched alkyl having 1 to 20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, where one or two of the substituents R3 to R7 may be fully substituted by halogens, in particular —F and/or —Cl, and one or more of the substituents R3 to R7 may be partially substituted by halogens, in particular —F and/or —Cl, and/or by —OH, —OR′, —N(R′)2, —CN, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′)2, —SO2N(R′)2, —C(O)X, —SO2OH, —SO2X, —SR′, —S(O)R′, —SO2R′, —NO2 and where one or two non-adjacent carbon atoms in R3 to R7 which are not in the α-position may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —SO2O—, —C(O)—, —C(O)O—, —N+(R′)2—, —P(O)R′O—, —C(O)NR′—, —SO2NR′—, —OP(O)R′O—, —P(O)(N(R′)2)NR′—, —P(R′)2═N— or —P(O)R′— where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and X each independently is halogen;
a guanidinium cation, which conforms to the formula (7)
[C(NR8R9)(NR10R11)(NR12R13)]+ (7),
where
R8 to R13 each, independently of one another, denote
H, —CN, N(R′)2, —OR′,
straight-chain or branched alkyl having 1 to 20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by straight-chain or branched alkyl groups having 1-6 C atoms, where one or two of the substituents R8 to R13 may be fully substituted by halogens, in particular —F and/or —Cl, and one or more of the substituents R8 to R13 may be partially substituted by halogens, in particular —F and/or —Cl, and/or by —OH, —OR′, —N(R′)2, —CN, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′)2, —SO2N(R′)2, —C(O)X, —SO2OH, —SO2X, —SR′, —S(O)R′, —SO2R′, —NO2 and where one or two non-adjacent carbon atoms in R8 to R13 which are not in the α-position may be replaced by atoms and/or atom groups selected from the group —O—, —S—, —S(O)—, —SO2—, —SO2O—, —C(O)—, —C(O)O—, —N+(R′)2—, —P(O)R′O—, —C(O)NR′—, —SO2NR′—, —OP(O)R′O—, —P(O)(N(R′)2)NR′—, —P(R′)2═N— or —P(O)R′—, where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and X each independently is halogen;
a heterocyclic cation which conforms to the formula (8)
[HetN]z+ (8)
where
HetNz+ denotes a heterocyclic cation selected from the group
where the substituents
R1′ to R4′ each, independently of one another, denote
H,
straight-chain or branched alkyl having 1-20 C atoms,
straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
straight-chain or branched alkynyl having 2-20 C atoms and one or more triple bonds,
and
R2′ denote additionally F, Cl, Br, I, —CN, —OR′, —N(R′)2, —P(O)(R′)2, —P(O)(OR′)2, —P(O)(N(R′)2)2, —C(O)R′, —C(O)OR′, —C(O)X, —C(O)N(R′)2, —SO2N(R′)2, —SO2OH, —SO2X, —SR′, —S(O)R′, —SO2R′ and/or NO2, with the proviso that R1′, R3′, R4′ are in this case independently of each other H and/or a straight-chain or branched alkyl having 1-20 C atoms, straight-chain or branched alkenyl having 2-20 C atoms and one or more double bonds,
where one to three substituents R1′ to R4′ may be fully substituted by halogens, in particular —F and/or —Cl, and one or more substituents R1′ to R4′ may be partially substituted by halogens, in particular —F and/or —Cl, and/or by —OH, —OR′, N(R′)2, —CN, —C(O)OH, —C(O)OR′, —C(O)R′, —C(O)N(R′)2, —SO2N(R′)2, —C(O)X, —SO2OH, —SO2X, —SR′, —S(O)R′, —SO2R′, —NO2, but where R1′ and R4′ cannot simultaneously be fully substituted by halogens and where, in the substituents R1′ to R4′, one or two non-adjacent carbon atoms which are not bonded to the heteroatom may be replaced by atoms and/or atom groups selected from the —O—, —S—, —S(O)—, —SO2—, —SO2O—, —C(O)—, —C(O)O—, —N+(R′)2—, —P(O)R′O—, —C(O)NR′—, —SO2NR′—, —OP(O)R′O—, —P(O)(N(R′)2)NR′—, —P(R′)2═N— or —P(O)R′—,
where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and X each independently is halogen or
a iodonium cation which conforms to the formula (9)
where
the aryl group Ar denotes each independently of each other aryl with 6 to 30 C atoms which is non-substituted or substituted with at least a straight-chain or branched alkyl group having 1 to 20 C atoms, a straight-chain or branched alkenyl group having 2 to 20 C atoms and one or more double bonds, a straight-chain or branched alkynyl group having 2 to 20 C atoms and one or more triple bonds, R1*, NO2, SR′, N(R′)2, CN and/or halogen and
where R′ each independently is H, non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl and
where R1* each independently is non-fluorinated, partially fluorinated or perfluorinated straight-chain or branched C1- to C18-alkyl, saturated C3- to C7-cycloalkyl, non-substituted or substituted phenyl
and halogen is F, Cl, Br or I,
with the proviso that potassium(18-crone-6)tricyano-n-octylborate and tetraethylammonium phenyl-tricyanoborate are excluded.

### Claim 2 (depends on 1)

A compound of formula I according to claim 1, characterized in that R1 in formula I is each independently a straight-chain or branched alkyl group having 1 to 4 C atoms, which optionally may contain at least one Br atom or at least one CN group or at least one oxygen atom or a straight-chain or branched alkenyl having 2 to 4 C atoms.

### Claim 3 (depends on 1)

Process for the preparation of a compound of formula I according to claim 1 in which [Kt]z+ is an alkali metal cation, z denotes 1 and the sum of x+y+v denotes 3, which denotes a compound of formula I-1,
[Me]+[(R1)4−x−y−zB(CN)x(NC)yFv]− I-1,
in which [Me]+ denotes an alkali metal cation and R1, x, y and v have a meaning according to claim 1,
comprising the reaction of a compound of formula II
[Me]+[(R1)BF3]− II
in which [Me]+ denotes an alkali metal cation and R1 has a meaning according to claim 1 with trialkylsilylcyanide, in which the alkyl groups are each independently of one another straight-chain or branched alkyl having 1 to 8 C atoms.

### Claim 4 (depends on 1)

Process for the preparation of a compound of formula I according to claim 1 in which [Kt]z+ is an organic cation and the sum of x+y+v denotes 3, comprising the reaction of a compound of formula III
[Kt]z+[(R1)BF3]− III
in which [Kt]z+ denotes the organic cation and R1 has a meaning according to claim 1 with trialkylsilylcyanide, in which the alkyl groups are each independently of one another straight-chain or branched alkyl having 1 to 8 C atoms.

### Claim 5 (depends on 1)

Process for the preparation of a compound of formula I according to claim 1 in which [Kt]z+ is alkali metal cation, z denotes 1 and the sum of x+y+v denotes 2, comprising the reaction of a compound of formula IV
(R1)2BOCH3 IV
in which R1 has a meaning according to claim 1 with trialkylsilylcyanide in the presence of an alkali metal fluoride, wherein the alkyl groups within the trialkylsilylcyanide are each independently of one another straight-chain or branched alkyl having 1 to 8 C atoms.

### Claim 6 (depends on 1)

Process for the preparation of a compound of formula I according to claim 1 in which [Kt]z+ is another cation than the used alkali metal cation in the starting material in a salt-exchange reaction, characterized in that an alkali metal salt of formula I-1
[Me]+[(R1)4−x−y−zB(CN)x(NC)yFv]− I-1
in which [Me]+ is an alkali metal cation and R1, x, y, v and the sum of x+y+v have a meaning according to claim 1 is reacted with a compound of formula V
KtA V,
in which
Kt has a meaning of an organic cation or an inorganic cation other than the alkali metal cation of the compound of formula I-1 and
A denotes F−, Cl−, Br−, I−, OH−, [HF2]−, [CN]−, [SCN]−, [R1COO]−, [R1OC(O)O]−, [R1SO3]−, [R2COO]−, [R2SO3]−, [R1OSO3]−, [BF4]−, [PF6]−, [HSO4]1−, [NO3]−, [(R2)2P(O)O]−, [R2P(O)O2]2−, [(R1O)2P(O)O]−, [(R1O)P(O)O2]2−, [(R1O)R1P(O)O]−, tosylate, malonate which may be substituted by straight-chain or branched alkyl groups having 1 to 4 C atoms, [HOCO2]− or [CO3]2− (merely for the synthesis of other compounds of formula I-1 having an other alkali metal cation than the starting material),
in which R1 is each independently of another a straight-chain or branched alkyl group having 1 to 12 C atoms and
R2 is each independently of one another a straight-chain or branched perfluorinated alkyl group having 1 to 12 C atoms and where electroneutrality should be taken into consideration in the formula of the salt KtA.

### Claim 7 (depends on 1)

An electrolyte formulation comprising at least one compound of formula I according to claim 1.

### Claim 8 (depends on 7)

An electrochemical and/or optoelectronic device comprising an electrolyte formulation according to claim 7.

### Claim 9 (depends on 1)

A catalyst, conducting salt, electrolyte, surfactant, phase-transfer catalyst, entrainer, extractant; antistatic additive, plasticizer; heat-transfer-medium, modifier for membranes and textile materials; lubricant, or hydraulic fluid comprising a compound of formula I according to claim 1 in which [Kt]z+ is an organic cation or H+ and z is 1, 2, 3 or 4.

### Claim 10 (depends on 7)

An electrolyte according to claim 7, in which [Kt]zt is Li+ as conducting salt and/or component of electrolytes.

### Claim 11 (depends on 1)

A catalyst, conducting salt, electrolyte, surfactant, phase-transfer catalyst, or antistatic additive comprising a compound of formula I according to claim 1 in which [Kt]z+ is an inorganic cation.

### Claim 12 (depends on 6)

A process according to claim 6, in which [Kt]z+ is an organic cation and z is 1, 2, 3 or 4.

### Claim 13 (depends on 1)

A cationic polymerization initiator, photo-polymerization initiator or photo-acid generator comprising a compound of formula I according to claim 1 in which [Kt]z+ is a cation of formula (2), (5), (6), (9), tritylium, pyrylium, 1-benzopyrylium or 2-benzopyrylium.

### Claim 14 (depends on 1)

Curable composition comprising at least one compound of formula I with cations of formula (2), (5), (6), (9), tritylium, pyrylium, 1-benzopyrylium or 2-benzopyrylium according to claim 1 and at least one polymerizable compound.